According to the Application for the Grant in 1992, (1) the preparation of modified heteropolyanion-supports and (2) the preparations of organometallic cation-species and the heteropolyanion-supported organometallic compounds have been performed. Something new results obtained from this research are as follows :1. For Dawson-type modified heteropolyanion [P_2W_<15>Nb_3O_<62>]^<9->, the previously reported (Bu_4N)_9 salt was acetonitrile-soluble and non-crystalline, and the crystalline Na_9 salt was obtained unexpectedly with - 20 mg order yield, the structure of which has been determined by a single- crystal X-ray diffraction analysis. In this research, a water-soluble and crystalline from of the Na_9 salt has been successfully isolated with synthetic scale (13 g, 61 % yield) as Na_9[P_2W_<15>Nb_3O_<62>]・23H_2O. This compound can be used as a new support for organometallic cation-species which will develop into the synthesis of a crystalline form of the heteropolyanion-supported organo
… Moremetallic compound, and can be also utilized as a homogeneous oxidation-catalyst.2. For Keggin-type modified heteropolyanion [SiW_9Nb_3O_<40>]^<7->, a water-soluble crystalline Na_7 salt has been first isolated with synthetic scale (3 g, 62 % yield) as Na_7[SiW_9Nb_3O_<40>]・16H_2O. This Na_7 salt can develop into the syntheses of crystalline heteropolyanion-supported organometallics and itself can also be utilized as a homegeneous oxidation-catalyst.3. New heteropolyanion-supported organometallic compound (Bu_4N)_4Na_3[Cp^*Rh・P_2W_<15>Nb_3O_<62>] (Cp^* = C_5Me_5) has been synthesized using a Dawson-type modified hetero-poly compound (Bu_4N)_9[P_2W_<15>Nb_3O_<62>] and a separately prepared organometallic complex [Cp^*RhCl_2]_2. Although this compound is not crystalline yet, an isolation of the crystalline form of [Cp^*Rh・P_2W_<15>Nb_3O_<62>]^<7-> will be promised using the above Na_9[P_2W_<15>Nb_3O_<62>]・23H_2O salt.今後、1.および2.で得られた二つの修飾ヘテロポリアニオン担体のNa塩を用いて有機金属種担持ヘテロポリ化合物の合成および結晶化を試みる予定である。 Less